JPH05345832A - Sustained releasing membrane - Google Patents
Sustained releasing membraneInfo
- Publication number
- JPH05345832A JPH05345832A JP15677892A JP15677892A JPH05345832A JP H05345832 A JPH05345832 A JP H05345832A JP 15677892 A JP15677892 A JP 15677892A JP 15677892 A JP15677892 A JP 15677892A JP H05345832 A JPH05345832 A JP H05345832A
- Authority
- JP
- Japan
- Prior art keywords
- sustained
- film
- polyolefin
- release
- stretching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Cosmetics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、徐放性膜に関し、更に
詳細には、延伸法によって得られる貫通微細孔を有する
ポリオレフィン製徐放性膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sustained-release film, and more particularly to a polyolefin sustained-release film having penetrating fine pores obtained by a stretching method.
【０００２】[0002]
【従来の技術】従来、徐放性を要求される物品として
は、室内及び車内等で用いられる芳香剤、防カビ剤及び
防虫剤等が良く知られており、これら物品の徐放性は、
以下に示すような方法により付与されていた。即ち、
薬剤をフェルト等の不織布に含浸させ、徐々に揮散さ
せる。 薬剤をポリエチレン等の袋に封入し、滲出さ
せた後に揮散させる。 薬剤をガーガム類等のゲル化
剤と混和させる。 薬剤を溶剤により希釈し、揮散し
易い状態にしてガラス瓶等の容器に保存する。なお、薬
剤を水に可溶化したものでは瓶にフェルト棒を挿入して
揮散を促進させている。2. Description of the Related Art Heretofore, as articles requiring sustained release, fragrances, fungicides and insect repellents used indoors and in vehicles are well known.
It was provided by the following method. That is,
A non-woven fabric such as felt is impregnated with the chemical and is gradually evaporated. The drug is enclosed in a bag of polyethylene or the like, exudes and then volatilizes. The drug is mixed with a gelling agent such as guar gum. Store the drug in a container such as a glass bottle after diluting the drug with a solvent and making it easy to volatilize. In the case of a drug solubilized in water, a felt rod is inserted into the bottle to promote volatilization.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うな従来法による芳香剤等においては、及び方法に
よる芳香剤等にあっては、簡便な形式ではあるが、香料
成分の内、揮散し易い成分のみが先に消失し、使用中に
香りが変化してきてしまうという課題があった。また、
の方法によるものについては、及びの欠点に加
え、使用中に徐々に表面が固化し、香りが揮散しにくく
なるという課題があった。更に、の方法によるものに
ついては、、及びの方法による欠点は若干改善さ
れているものの、容器の転倒により中味が流出するおそ
れがあるという課題があった。However, in the fragrance and the like by such a conventional method, and in the fragrance and the like by the method, although it is a simple form, a component which is easily volatilized among the fragrance components. However, there was a problem that the only one disappeared first and the scent changed during use. Also,
In addition to the disadvantages of and, there is a problem that the surface is gradually solidified during use and the fragrance is less likely to be volatilized. Further, with respect to the method (1), although the drawbacks due to the method (1) and (2) are slightly improved, there is a problem that the contents may flow out when the container falls.
【０００４】一方、ポリオレフィンフィルムを延伸処理
等して微多孔質平膜を得る方法は、米国特許第３,５５
８,７６４号明細書、特公昭４６−４０１１９号公報及
び特公昭５０−３２５３１号公報に開示されているが、
これらの方法により得られる平膜は、空孔の形状及び大
きさ等が不均一であるため、前記香料等の薬剤を保持さ
せたとしても液洩れが生じたり、これら薬剤の成分を均
一に長時間揮散させることは極めて困難であり、徐放性
膜として用いるには不向きであり、余り考慮されていな
かった。本発明は、このような従来技術の有する課題に
鑑みてなされたもので、その目的とするところは、前記
香料等の薬剤を確実に保持し、保持した薬剤の成分を均
一かつ有効な濃度及び速度で揮散できる徐放性膜を提供
することにある。On the other hand, a method for obtaining a microporous flat membrane by stretching a polyolefin film is disclosed in US Pat. No. 3,553.
Although disclosed in Japanese Patent Publication No. 8,764, Japanese Patent Publication No. 46-40119 and Japanese Patent Publication No. 50-32531,
The flat membranes obtained by these methods have non-uniform pores such as shape and size. Therefore, even if the chemicals such as the fragrance are held, liquid leakage may occur or the components of these chemicals may be uniformly dispersed. It was extremely difficult to volatilize it for a long time, and it was unsuitable for use as a sustained-release film, and was not considered so much. The present invention has been made in view of the above problems of the prior art, the object is to reliably hold the drug such as the fragrance, a uniform and effective concentration of the components of the drug held and It is to provide a sustained-release film that can be volatilized at a speed.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究した結果、形状及び大きさの均一
な貫通孔を備え、所定の空孔率等を有するポリオレフィ
ン膜により前記課題が解決されることを見いだし、本発
明を完成するに至った。従って、本発明の徐放性膜は、
ポリオレフィンフィルムを延伸して得られる徐放性膜で
あって、形状及び大きさが均一な貫通微細孔を有し、空
孔率が５〜２０％、孔径が０．０１〜０．０８μｍ、累
積比表面積が２５〜５０ｍ2／ｇ、窒素ガス透過量が１
５０ｌ／ｍｉｎ・ｍ2・ｋｇ／ｃｍ2以下であることを特
徴とする。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polyolefin film having through holes of uniform shape and size and having a predetermined porosity is used. The inventors have found that the problems are solved and have completed the present invention. Therefore, the sustained-release membrane of the present invention is
A sustained-release film obtained by stretching a polyolefin film, which has penetrating micropores having a uniform shape and size, a porosity of 5 to 20%, a pore diameter of 0.01 to 0.08 μm, and an accumulation. Specific surface area of 25-50 m 2 / g, nitrogen gas permeation amount of 1
It is characterized in that it is 50 l / min · m 2 · kg / cm 2 or less.
【０００６】[0006]
【作用】本発明の徐放性膜は、形状及び大きさが均一な
貫通微細孔を有するため、保持した薬剤を均一に揮散さ
せることができる。また、貫通微細孔の大きさ、空孔率
等を所定の大きさに調整したため保持した薬剤を有効に
活用することができる。The sustained-release membrane of the present invention has penetrating micropores having a uniform shape and size, so that the retained drug can be vaporized uniformly. Further, since the size of the penetrating fine holes, the porosity, etc. are adjusted to a predetermined size, the held drug can be effectively used.
【０００７】以下、本発明の徐放性膜の製造方法につい
て説明する。本発明の徐放性膜の製造に用いるポリオレ
フィンとしては、高密度ポリエチレン、ポリプロピレ
ン、ポリ（４−メチルペンテン−１）を挙げることがで
き、特にポリプロピレンが好ましい。ポリプロピレンを
用いる場合は、特に限定されるものではなく、プロピレ
ンの単独重合体のみならず、プロピレンと他のモノマー
又はオリゴマーとのランダム、ブロック及びグラフト共
重合体も含まれる。The method for producing the sustained-release film of the present invention will be described below. Examples of the polyolefin used for producing the sustained-release membrane of the present invention include high-density polyethylene, polypropylene, and poly (4-methylpentene-1), and polypropylene is particularly preferable. When polypropylene is used, it is not particularly limited and includes not only propylene homopolymer but also random, block and graft copolymers of propylene and other monomers or oligomers.
【０００８】また、使用するポリオレフィンのＭＦＩ
（メルトフローインデックス）又はＭＩ（メルトインデ
ックス）は、フィルムが形成可能な範囲であれば特に限
定されるものではないが、ポリプロピレンを用いる場合
にはフィルムの形成や生産性を考慮すると、ＭＦＩが
０．７〜３０ｇ／１０分のものを用いるのが好ましい。
その他、可塑剤、着色剤、難燃化剤、充填剤等の添加剤
（材）を含むポリオレフィンも使用することができる。Also, the MFI of the polyolefin used
(Melt flow index) or MI (melt index) is not particularly limited as long as a film can be formed. However, when polypropylene is used, MFI is 0 in consideration of film formation and productivity. It is preferable to use the one of 0.7 to 30 g / 10 minutes.
In addition, a polyolefin containing an additive (material) such as a plasticizer, a colorant, a flame retardant, and a filler can also be used.
【０００９】本発明においては、まず公知のフィルム製
造法に従って成形し、未延伸ポリオレフィンフィルムを
作成する。利用できるフィルム製造法の例としては、イ
ンフレーションフィルム成形法、Ｔダイフィルム成形法
等を挙げることができる。このような成形法における成
形条件は公知技術により適宜選択することができる。例
えば、フィルム成形温度は、ポリオレフィンを吐出する
ことができる温度以上であって、ポリオレフィンの熱分
解温度以下の範囲内で行うことができる。ポリオレフィ
ンとしてポリプロピレンを用いる場合には、通常では１
７０〜３００℃、好ましくは１８０〜２７０℃、高密度
ポリエチレンを用いる場合には、通常１５０〜３００
℃、好ましくは１６０〜２７０℃、ポリ（４−メチルペ
ンテン−１）を使用する場合には、通常では２６０〜３
３０℃、好ましくは２７０〜３００℃である。In the present invention, first, an unstretched polyolefin film is formed by molding according to a known film manufacturing method. Examples of film manufacturing methods that can be used include an inflation film molding method and a T-die film molding method. The molding conditions in such a molding method can be appropriately selected by a known technique. For example, the film forming temperature may be a temperature above which the polyolefin can be discharged and below the thermal decomposition temperature of the polyolefin. When polypropylene is used as the polyolefin, it is usually 1
70 to 300 ° C., preferably 180 to 270 ° C. When using high density polyethylene, usually 150 to 300
C., preferably 160-270.degree. C., when using poly (4-methylpentene-1) it is usually 260-3.
30 degreeC, Preferably it is 270-300 degreeC.
【００１０】また、成形して得られる未延伸ポリオレフ
ィンフィルムの結晶配向性が極度に低い場合には、本発
明における特異な孔構造を有する徐放性膜を得ることは
できない。従って、前記吐出温度以外に、ドラフト比と
しては生産性も考慮して１０〜６０００の範囲が好まし
く、また、冷却媒体の種類、吐出された樹脂が冷却媒体
と接触するまでの時間、距離、その時の樹脂の温度等も
十分考慮してフィルムを成形する必要がある。Further, when the crystal orientation of the unstretched polyolefin film obtained by molding is extremely low, it is not possible to obtain a sustained-release film having a unique pore structure in the present invention. Therefore, in addition to the discharge temperature, the draft ratio is preferably in the range of 10 to 6000 in consideration of productivity, and the type of cooling medium, the time until the discharged resin comes into contact with the cooling medium, the distance, It is necessary to form the film by sufficiently considering the temperature of the resin and the like.
【００１１】得られた未延伸ポリオレフィンフィルムは
延伸工程に付する前に熱処理してもよく、この延伸前の
熱処理を行うことにより、未延伸ポリオレフィンフィル
ムの結晶化度を向上することができるため、延伸により
得られる徐放性膜の特性は更に向上する。この熱処理
は、未延伸ポリオレフィンフィルムを、例えばポリオレ
フィンの融解温度より１５〜７０℃低い温度に加熱した
空気中で３秒間以上加熱することにより行うことができ
る。The obtained unstretched polyolefin film may be heat-treated before being subjected to a stretching step, and the heat treatment before stretching can improve the crystallinity of the unstretched polyolefin film. The characteristics of the sustained release film obtained by stretching are further improved. This heat treatment can be performed by heating the unstretched polyolefin film for 3 seconds or more in air heated to a temperature 15 to 70 ° C. lower than the melting temperature of the polyolefin.
【００１２】本発明に係る延伸工程には、結晶化度が５
０〜９０％、好ましくは６０〜９０％であり、かつ小角
Ｘ線散乱の回折像が２点図形で各図形は略円形であり各
図形における回折強度の半価幅が２５′以下、好ましく
は２０′以下であって長周期が１２０オングストローム
以上、好ましくは１５０オングストローム以上である未
延伸ポリオレフィンを用いる。In the stretching step according to the present invention, the crystallinity is 5
0 to 90%, preferably 60 to 90%, and the diffraction image of small-angle X-ray scattering is a two-point figure, each figure is substantially circular, and the half-value width of the diffraction intensity in each figure is 25 'or less, preferably An unstretched polyolefin having a length of 20 'or less and a long period of 120 Å or more, preferably 150 Å or more is used.
【００１３】延伸処理は、使用するポリオレフィンの融
解温度より１０〜１００℃低い温度範囲で、延伸歪速度
５０〜５０００％／分未満、好ましくは５００〜２００
０％／分未満で行う。ここで、ポリオレフィンとしてポ
リプロピレンを用いて延伸する場合には、その温度範囲
を９０〜１５０℃とするのが好ましい。The stretching treatment is carried out in a temperature range 10 to 100 ° C. lower than the melting temperature of the polyolefin used, and a stretching strain rate of 50 to less than 5000% / min, preferably 500 to 200.
Perform at less than 0% / min. When polypropylene is used as the polyolefin for stretching, the temperature range is preferably 90 to 150 ° C.
【００１４】以下、本発明に係る延伸方法について更に
詳細に説明する。この場合の延伸工程は、ポリオレフィ
ンの融解温度より１０〜１００℃低い温度範囲、好まし
くは２０〜８０℃低い温度範囲において、延伸歪速度５
０〜５０００％／分未満で行う。例えば、ポリプロピレ
ンを使用する場合は、通常９０〜１６０℃、好ましくは
９０〜１５０℃、高密度ポリエチレンを使用する場合に
は通常５０〜１００℃、ポリ（４−メチルペンテン−
１）を使用する場合には通常１５０〜２００℃の温度範
囲で行う。The stretching method according to the present invention will be described in more detail below. In the stretching step in this case, the stretching strain rate is 5 in a temperature range 10 to 100 ° C. lower than the melting temperature of the polyolefin, preferably 20 to 80 ° C. lower.
It is performed at 0 to less than 5000% / min. For example, when polypropylene is used, it is usually 90 to 160 ° C., preferably 90 to 150 ° C. When high density polyethylene is used, it is usually 50 to 100 ° C., poly (4-methylpentene-).
When 1) is used, it is usually performed in a temperature range of 150 to 200 ° C.
【００１５】前記温度範囲を外れた温度で延伸すると、
温度が低い場合には貫通孔が無くなり好ましくない。一
方、温度が高い場合には、膜厚や延伸方向に垂直な膜幅
のいずれもが小さくなったり、ポリオレフィンが融解又
は部分融解し、孔が形成されなかったり、孔が潰れるこ
とが起こり好ましくない。When stretched at a temperature outside the above temperature range,
When the temperature is low, there are no through holes, which is not preferable. On the other hand, when the temperature is high, both the film thickness and the film width perpendicular to the stretching direction are reduced, the polyolefin is melted or partially melted, pores are not formed, or the pores are collapsed, which is not preferable. ..
【００１６】また、延伸歪速度が５０００％／分以上で
あると、貫通孔が無くなったり、孔が全く生じないこと
が起こり好ましくない。延伸歪速度が５０％／分未満で
あると、孔の平均孔径、空孔率は延伸倍率に応じて大き
くなり過ぎる。延伸倍率は、目的とするポリオレフィン
製徐放性膜の使用目的に応じた孔の平均孔径に対応させ
て変更することができる。延伸倍率は未延伸ポリオレフ
ィンフィルムの初期長さに対して２０〜９０％、好まし
くは３０〜５０％である。延伸倍率が６０％を超える
と、空孔率、孔径が大きくなり、ガス透過量が多くなり
好ましくない。If the stretching strain rate is 5000% / min or more, the through holes may disappear or no holes may be generated, which is not preferable. When the stretching strain rate is less than 50% / min, the average pore diameter and porosity of the pores become too large depending on the stretching ratio. The draw ratio can be changed according to the average pore diameter of the pores depending on the intended use of the intended polyolefin sustained-release membrane. The stretching ratio is 20 to 90%, preferably 30 to 50%, based on the initial length of the unstretched polyolefin film. When the stretching ratio exceeds 60%, the porosity and the pore diameter increase, and the gas permeation amount increases, which is not preferable.
【００１７】前記延伸工程を経て多孔質化したポリオレ
フィンフィルムは、次いで熱処理することが好ましい。
この熱処理は、形成した微細孔を保持するための熱固定
を主たる目的とするものである。この熱処理は、延伸状
態を保持したまま多孔質化したポリオレフィンフィルム
を空気中で３秒以上、使用したポリオレフィンの融解温
度より５〜６０℃低い温度に加熱すること等により行う
ことができる。具体的な加熱温度としては、ポリプロピ
レンを使用する場合には通常１１０〜１６５℃、好まし
くは１３０〜１５５℃、高密度ポリエチレンを使用する
場合には通常７０〜１２５℃、好ましくは８０〜１２０
℃、ポリ（４−メチル−ペンテン−１）を使用する場合
には通常１５０〜２１０℃、好ましくは１６０〜２００
℃である。The polyolefin film made porous through the stretching step is preferably heat-treated next.
The main purpose of this heat treatment is heat fixation for holding the formed fine pores. This heat treatment can be performed by heating the porous polyolefin film while maintaining the stretched state in the air for 3 seconds or more to a temperature 5 to 60 ° C. lower than the melting temperature of the used polyolefin. As a specific heating temperature, when polypropylene is used, it is usually 110 to 165 ° C., preferably 130 to 155 ° C. When high density polyethylene is used, it is usually 70 to 125 ° C., preferably 80 to 120.
℃, when using poly (4-methyl-pentene-1), usually 150 ~ 210 ℃, preferably 160 ~ 200
℃.
【００１８】加熱温度が前記の上限温度より高いと、形
成された孔が閉鎖することもあり、また温度が上記の下
限温度より低いか又は加熱時間が３秒より短いと熱固定
が不十分となり易く、後に孔が閉鎖し、また使用に際し
ての温度変化により熱収縮を起こし易くなり好ましくな
い。また、この時の緩和率は０〜２５％である。If the heating temperature is higher than the above-mentioned upper limit temperature, the formed pores may be closed, and if the temperature is lower than the above-mentioned lower limit temperature or the heating time is shorter than 3 seconds, heat fixation becomes insufficient. It is not preferable because the holes tend to be closed, the holes are closed later, and thermal contraction easily occurs due to a temperature change during use. The relaxation rate at this time is 0 to 25%.
【００１９】前述の方法により得られた徐放性膜は、形
状及び大きさ等が従来の多孔質膜と比較して極めて均一
な貫通孔を備える。また、この徐放性膜の空孔率、孔径
及び累積比表面積の値は、適用すべき芳香剤、防カビ剤
及び防虫剤等に応じて適宜変更することができる。この
徐放性膜を芳香剤に用いる場合には、使用する香料液の
組成・性質等により適宜変更し得るが、５〜２０％の空
孔率、０．０１〜０．０８μｍの孔径及び２５〜５０ｍ
2の累積比表面積、１５０ｌ／ｍｉｎ・ｍ2・ｋｇ／ｃｍ
2以下の窒素ガス透過量を有するのが好ましい。空孔
率、孔径、累積比表面積及び窒素ガス透過量の値が、前
記の値の下限を下回ると香料液が極めて蒸発しにくく、
上限を超えると蒸発速度が大きく、かつ膜表面に結露
（凝縮又は滲み）、液洩れが生じ好ましくない。The sustained-release film obtained by the above-mentioned method has through-holes whose shape and size are extremely uniform as compared with the conventional porous film. The porosity, pore size and cumulative specific surface area of the sustained-release film can be appropriately changed depending on the aromatic, fungicide, insect repellent, etc. to be applied. When this sustained-release film is used as a fragrance, the porosity of 5 to 20%, a pore size of 0.01 to 0.08 μm, and a pore size of 25 can be appropriately changed depending on the composition and properties of the fragrance liquid to be used. ~ 50m
2 cumulative specific surface area, 150 l / min · m 2 · kg / cm
It preferably has a nitrogen gas permeability of 2 or less. If the porosity, pore diameter, cumulative specific surface area and nitrogen gas permeation value are below the lower limits of the above values, the perfume liquid is extremely difficult to evaporate,
If it exceeds the upper limit, the evaporation rate is high, and dew condensation (condensation or bleeding) occurs on the film surface, resulting in liquid leakage, which is not preferable.
【００２０】[0020]
【実施例】以下、本発明を実施例及び比較例により詳細
に説明する。 （徐放性膜の調製） （実施例１〜８）ポリプロピレン（ＵＢＥ−ＰＰ−Ｆ１
０３ＥＡ、商品名：宇部興産（株）製、ＭＦＩ＝３．５
ｇ／１０分）を、幅７５０ｍｍのダイスを備えたＴダイ
成形機を使用し、吐出温度１８５℃、引取速度４０ｍ／
分の条件で処理しロールフィルムを成形した。得られた
ポリプロピレンフィルムを１５０℃の加熱ロールで４分
加熱処理することにより、結晶化度が７２％、小角Ｘ線
散乱の回折像が２点図形で各図形は略円形であり回折強
度の半価幅が１５′であって長周期が２２０オングスト
ロームである未延伸ポリプロピレンフィルムを得た。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. (Preparation of Sustained Release Film) (Examples 1 to 8) Polypropylene (UBE-PP-F1)
03EA, product name: Ube Industries, Ltd., MFI = 3.5
g / 10 min) using a T-die molding machine equipped with a die having a width of 750 mm, a discharge temperature of 185 ° C., a take-up speed of 40 m /
The roll film was formed by processing under the condition of minutes. By subjecting the obtained polypropylene film to heat treatment with a heating roll at 150 ° C. for 4 minutes, the crystallinity is 72%, the diffraction image of small-angle X-ray scattering is a two-point figure, and each figure is substantially circular and has a diffraction intensity of half a half. An unstretched polypropylene film having a valence of 15 'and a long period of 220 Å was obtained.
【００２１】この未延伸フィルムを加熱ロール（１３０
℃）中で、７８１〜１０４２％／分の歪速度にて初期長
さに対して３０％延伸し、更に延伸状態を保持したまま
１５０℃の加熱空気槽内で７秒間熱固定処理を行い、多
孔質のポリプロピレン製徐放性膜を調製した。この時の
緩和率は０〜１５％である。多孔質のポリプロピレン製
徐放性膜を調製した。得られた徐放性膜の空孔率、孔径
及び累積比表面積は、カンタクロム社（米国）製のオー
トスキャン３３を用い水銀圧入法で測定した。また、窒
素ガス透過量は、有効透過面積１．２６×１０-3ｍ2の
フィルムホルダーに試料フィルムを装着し、１ｋｇ／ｃ
ｍ2の圧力で窒素ガスを供給して１分間に透過するガス
量を測定し、次式にて求めた。 窒素ガス透過量（ｌ／ｍｉｎ・ｍ2・ｋｇ／ｃｍ2）＝１
分間のガス透過量／有効膜面積 測定結果を表１及び２に示す。This unstretched film was heated on a heating roll (130
C.) at a strain rate of 781 to 1042% / min, and stretched 30% with respect to the initial length, and further heat-treated for 7 seconds in a heated air tank at 150 ° C. while maintaining the stretched state. A porous polypropylene sustained-release membrane was prepared. The relaxation rate at this time is 0 to 15%. A porous polypropylene sustained-release membrane was prepared. The porosity, pore diameter and cumulative specific surface area of the obtained sustained release membrane were measured by mercury porosimetry using Autoscan 33 manufactured by Kantachrome Co. (USA). The nitrogen gas permeation rate was 1 kg / c by mounting the sample film on a film holder with an effective permeation area of 1.26 × 10 −3 m 2.
Nitrogen gas was supplied at a pressure of m 2 and the amount of gas that permeated in 1 minute was measured and calculated by the following formula. Nitrogen gas permeation rate (l / min · m 2 · kg / cm 2 ) = 1
The gas permeation amount / minute effective membrane area measurement results are shown in Tables 1 and 2.
【００２２】（比較例１及び２）１３０℃の加熱槽又は
加熱ロールで、歪速度をそれぞれ３５及び２６％／分と
し、初期長さに対して６０％及び２００％で延伸した以
外は、実施例１と同様の処理を行い、所定の空孔率、孔
径及び累積比表面積を有する多孔質膜を得た。これら膜
の空孔率等の測定結果を表１及び２に示す(Comparative Examples 1 and 2) In Comparative Examples 1 and 2 except that the strain rate was 35 and 26% / min in a heating tank or a heating roll at 130 ° C. and stretching was performed at 60% and 200% with respect to the initial length, respectively. The same treatment as in Example 1 was performed to obtain a porous membrane having a predetermined porosity, pore diameter and cumulative specific surface area. The measurement results of the porosity of these films are shown in Tables 1 and 2.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】（徐放性性能評価試験）前述のようにして
得られたそれぞれの徐放性膜を用い、ヒートシール処理
して６０×１００ｍｍの矩形袋を作製し、この袋に所定
の供試液５ｇを封入して、試験体を得た。得られた試験
体を縦長に吊り下げ、室温での重量変化を測定した。供
試液を表１及び２に示し、重量変化の様子を図１〜図３
に示す。図１〜図３に示したように、本発明の徐放性膜
を用いた場合には、良好な徐放性を示すことが分かる。
一方、比較例１及び２の徐放性膜から得られた試験体に
供試液を封入して同様の試験を行った結果、比較例１及
び２のいずれも場合にも、短時間で試験体から液洩れが
生じ、徐放性膜としては使用できないことが分かった。(Sustained release performance evaluation test) Using each of the sustained release membranes obtained as described above, a heat-sealing treatment was performed to prepare a rectangular bag of 60 × 100 mm, and the predetermined test solution was put in this bag. A test body was obtained by enclosing 5 g. The obtained test body was suspended vertically and the weight change at room temperature was measured. The test solutions are shown in Tables 1 and 2, and the changes in weight are shown in Figs.
Shown in. As shown in FIGS. 1 to 3, it can be seen that when the sustained release membrane of the present invention is used, excellent sustained release properties are exhibited.
On the other hand, as a result of carrying out a similar test by enclosing the test solution in the test bodies obtained from the sustained-release membranes of Comparative Examples 1 and 2, in both cases of Comparative Examples 1 and 2, the test bodies were tested in a short time. As a result, liquid leakage occurred and it could not be used as a sustained release membrane.
【００２６】なお、表１及び２において、供試液１は、
エタノールと水との混合液（４０：６０、重量比）であ
り、供試液２もエタノールと水との混合液（２０：８
０、重量比）である。また、香料液の配合組成（重量
部）は以下の通りである。 ポリオキシエチレン硬化ヒマシ油（６０ＥＯ）・・・・・・・・１０．０ ポリオキシエチレンノニルフェニルエーテル（１０ＥＯ）・・・２０．０ 香料・・・・・・・・・・・・・・・・・・・・・・・・・・・５０．０ ９５％アルコール・・・・・・・・・・・・・・・・・・・・４００．０ 精製水・・・・・・・・・・・・・・・・・・・・・・・・・５２０．０In Tables 1 and 2, the test solution 1 is
It is a mixed solution of ethanol and water (40:60, weight ratio), and the test solution 2 is also a mixed solution of ethanol and water (20: 8).
0, weight ratio). The composition of the fragrance liquid (parts by weight) is as follows. Polyoxyethylene hydrogenated castor oil (60EO) ・ ・ ・ ・ ・ ・ 10.0 Polyoxyethylene nonyl phenyl ether (10EO) ・ ・ ・ 20.0 Perfume ・ ・ ・ ・50.0 95% alcohol ... 400.0 Purified water ... 520.0
【００２７】以上、本発明を実施例により説明したが、
本発明はこれに限定されるものではなく、本発明の要旨
の範囲内で種々の変形が可能である。例えば、本発明の
徐放性膜は香料のみならず防カビ剤、防虫剤等にも適用
できる。また、供試液の配合組成・性質等に応じて、徐
放性膜の空孔率、孔径等を適宜変更することもできる。The present invention has been described above with reference to the embodiments.
The present invention is not limited to this, and various modifications can be made within the scope of the gist of the present invention. For example, the sustained-release film of the present invention can be applied not only to fragrances but also to fungicides, insect repellents and the like. Further, the porosity, the pore size, etc. of the sustained-release membrane can be appropriately changed depending on the composition and properties of the test solution.
【００２８】[0028]
【発明の効果】以上説明したように、本発明において
は、形状及び大きさの均一な貫通孔を備え、所定の空孔
率等を有するポリオレフィン膜により徐放性膜を構成す
ることとしたため、香料等の薬剤を確実に保持し、保持
した薬剤の成分を均一かつ有効な濃度及び速度で揮散で
きる徐放性膜を提供することができる。As described above, according to the present invention, the sustained-release film is constituted by the polyolefin film having the through holes of uniform shape and size and having the predetermined porosity and the like. It is possible to provide a sustained-release film capable of reliably holding a drug such as a fragrance and volatilizing the components of the held drug at a uniform and effective concentration and rate.
【図１】徐放性の性能を示す線図である。FIG. 1 is a diagram showing sustained-release performance.
【図２】徐放性の性能を示す線図である。FIG. 2 is a diagram showing sustained-release performance.
【図３】徐放性の性能を示す線図である。FIG. 3 is a diagram showing sustained-release performance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 嶋田 順一 大阪府枚方市中宮北町３番10号 宇部興産 株式会社枚方研究所内 (72)発明者 松尾 正太 東京都港区赤坂１丁目12番32号 宇部興産 株式会社東京本社内 (72)発明者 佐藤 昌弘 神奈川県横浜市保土ヶ谷区西久保町１の４ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Shimada 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries, Ltd. Hirakata Research Laboratory (72) Inventor Shota Matsuo 1-12-32 Akasaka, Minato-ku, Tokyo Ube Kosan Co., Ltd. Tokyo Head Office (72) Inventor Masahiro Sato 1-4 Nishikubo-cho, Hodogaya-ku, Yokohama-shi, Kanagawa
Claims (1)
れる徐放性膜であって、形状及び大きさが均一な貫通微
細孔を有し、空孔率が５〜２０％、孔径が０．０１〜
０．０８μｍ、累積比表面積が２５〜５０ｍ2／ｇ、窒
素ガス透過量が１５０ｌ／ｍｉｎ・ｍ2・ｋｇ／ｃｍ2以
下であることを特徴とする徐放性膜。1. A sustained-release film obtained by stretching a polyolefin film, which has penetrating micropores having a uniform shape and size, a porosity of 5 to 20%, and a pore diameter of 0.01 to.
A sustained release membrane having a 0.08 μm, a cumulative specific surface area of 25 to 50 m 2 / g, and a nitrogen gas permeation amount of 150 l / min · m 2 · kg / cm 2 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15677892A JP3019963B2 (en) | 1992-06-16 | 1992-06-16 | Sustained release membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15677892A JP3019963B2 (en) | 1992-06-16 | 1992-06-16 | Sustained release membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05345832A true JPH05345832A (en) | 1993-12-27 |
| JP3019963B2 JP3019963B2 (en) | 2000-03-15 |
Family
ID=15635112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15677892A Expired - Lifetime JP3019963B2 (en) | 1992-06-16 | 1992-06-16 | Sustained release membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3019963B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006183008A (en) * | 2004-12-28 | 2006-07-13 | Mitsui Chemicals Inc | Film excellent in permeability |
| JP2012523303A (en) * | 2009-04-16 | 2012-10-04 | ザ プロクター アンド ギャンブル カンパニー | Method for delivering volatile materials |
| JP2012523302A (en) * | 2009-04-16 | 2012-10-04 | ザ プロクター アンド ギャンブル カンパニー | Device for delivering volatile materials |
| US9439993B2 (en) | 2009-04-16 | 2016-09-13 | The Procter & Gamble Company | Apparatus for delivering a volatile material |
| JP2017038942A (en) * | 2009-04-16 | 2017-02-23 | ザ プロクター アンド ギャンブル カンパニー | Device for delivering volatile material |
| US10143766B2 (en) | 2009-04-16 | 2018-12-04 | The Procter & Gamble Company | Volatile composition dispenser |
| US11911540B2 (en) | 2009-04-16 | 2024-02-27 | The Procter & Gamble Company | Apparatus for delivering a volatile material |
-
1992
- 1992-06-16 JP JP15677892A patent/JP3019963B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006183008A (en) * | 2004-12-28 | 2006-07-13 | Mitsui Chemicals Inc | Film excellent in permeability |
| JP2012523303A (en) * | 2009-04-16 | 2012-10-04 | ザ プロクター アンド ギャンブル カンパニー | Method for delivering volatile materials |
| JP2012523302A (en) * | 2009-04-16 | 2012-10-04 | ザ プロクター アンド ギャンブル カンパニー | Device for delivering volatile materials |
| US9272063B2 (en) | 2009-04-16 | 2016-03-01 | The Procter & Gamble Company | Method for delivering a volatile material |
| US9439993B2 (en) | 2009-04-16 | 2016-09-13 | The Procter & Gamble Company | Apparatus for delivering a volatile material |
| JP2017038942A (en) * | 2009-04-16 | 2017-02-23 | ザ プロクター アンド ギャンブル カンパニー | Device for delivering volatile material |
| US9993574B2 (en) | 2009-04-16 | 2018-06-12 | The Procter & Gamble Company | Method for delivering a volatile material |
| US10143766B2 (en) | 2009-04-16 | 2018-12-04 | The Procter & Gamble Company | Volatile composition dispenser |
| US10500298B2 (en) * | 2009-04-16 | 2019-12-10 | The Procter & Gamble Company | Method for delivering a volatile material |
| US11517643B2 (en) | 2009-04-16 | 2022-12-06 | The Procter & Gamble Company | Apparatus for delivering a volatile material |
| US11911540B2 (en) | 2009-04-16 | 2024-02-27 | The Procter & Gamble Company | Apparatus for delivering a volatile material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3019963B2 (en) | 2000-03-15 |
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